Azodyestuff containing a nitrosogroup



Patented Jan, 9, 1934 UNITED STATE AZODYESTUFF CONTAINING A NITEOSOGROU? Leopold Laska, Arthur Zitscher, Wilhelm Christ,

and Adolf Peta-old,

Offenbach-on-the-Main,

Germany, assignors to General Aniiine Works, .Inc., New York, N. L, a corporation of Dela- N Drawing.

Application November 12, 1928,-

Serial No; 318,992, and in Germany December 22 Claims.

Our invention relates to azodyestuifs containing a nitrosogroup in their molecule and to a process of making same. The new dyestuffs cor respond probably to the general formula:

in which formula the naphthalene and the two benzene nuclei may contain further substituents other than a sulfonic or carboxylic acid group 1 and the benzene nucleus signified by 11 may be replaced by a naphthalene nucleus.

They are obtained by combining in substance or upon a substratum a l-diazo-N-nitrosodiarylamine compound not containing a sulfonic or carboxylic acid group and probably corresponding with thegeneral formula:

in which formula X means an anion and the two benzene nuclei may contain further substituents and the nucleus signified by II may be replaced by a naphthalene nucleus, with an arylide of 2.3- hydroxynaphthoic acid. The diazo-nitrosodiphenylaniine compounds, which have not been used hitherto for the production of azo-dyestuffs insoluble in water, are dist'nguishcd by their particular capacity for combining and the stability of their solutions, a fact, which is of importance for producing ice colors by means of a standard bath. These diazonitrosodiphenylamine compounds may be obtained by the action of two molecular proportions of an alkali nitrite on one molecular proportion of an aminodiphenylamine compound in a mineral acid solution.

The new azo-dyestuiis insoluble in water thus obtainable re when dry red to garnet colored powders, soluble concentrated sulfuric acid to a reddish violet to violet solution. When produced on the fiber they yield red to garnet to violet dyeings of a good fastness to chlorine and washing according to the character of the dyestuii produced.

Suitable for the present process are nitrosodiace-compounds of 4-aminodiphenylarnine itself and of its substitution products, such as i-amino- 2 methyldiphenylainine,- amino-2 unethoxydh *phenylamine, :A-amino-2'-ethoxydiphenylam ne,

-amino-Z-phenoxydiphenylamine, 4-amino-2- chlorodiphenylamine, 4-amino-3-me'tnyldiphenylamine, lamino 3-chlorodiphenylamine, 4- amino if methyldiphenylamine, =i-arnino 4' m thoxydiphenylaznine, e amino 4 ethoxydi phenylarnine, c amino i phenoxydiphenylamine, l-aminoi-ch1orodiphenylamine, a-amino- 3 -methyl-a -"nethoxydphenylamine, i-amino-B methyl 6 methoxydiphenylamine, l-amino-W- methyl- 4 chlorodiphenylamine, amino 2 methyl 5' chlorodiphenylamine, 4 amino-3 methyl 6' chlorodiphenylamine, 4 amino l methyl 3 chlorodiphenylamine, 4 amino -2 ni thoxy-4' -chlorodiphenylaminc, 4-amino-3' .4- dichiorodiphenylamine and l-aminophenid-fi- 7 naphthylamine.

As azccornponents there may be used, for instance, the 2.3-hydro-xynaphthoylderivatives of aniline, of toluidines, of aminoethylbenz enes, of the alkyl, aralkyl: and aryleethers of aminophenols, of aminophenylketones, -sulfones and -su1fainines, of the halogensubstitution products of the aforesaid compounds, of naphthylamines and their derivatives, of arylenediamines, diaminodiaryls and their derivatives, diamines, in s which two arylradicals are united by afurther" complex, further such arylamides of 2.3-hydroxynaphthoic acid containing further substituents with the exception of sulfonic or carbox- V ylic acid group in the hydroXynaphthoyl-radical 3 such as arylamides of 6bron1o-2.3hydroxynaphthoic acid.

In order to further illustrate our invention .the following examples are given, the partsbeing by Weight and all temperatures in centigrade degrees, but we wish it to be understood that we are not limited the particular products or reaction conditions mentioned therein.

Example 1 21A parts of laminolf-methoXy-diphenylamine are diazotized with 57Iparts of hydrochloric acid 20 B., 500 parts of water and 15.2 parts of sodium nitrite at about 5-102 whereby also a nitrosogroup is introduced. The free mineral 109 acid is nearly neutralized with sodium acetate and the solution of the 4-mcthoxy-N-nitrosodiphenylamine-4-diazonium chloride thus obtained as allowed to run at about 5-10 into a suspension obtained by dissolving 26.3 parts of the anilide of 2.3hydroxynaphthoic acid in .a sufficient quantity of a caustic soda solutionwith the addition of Turkey red oil and precipitating thesoiution by adding acetic acid. When the combination is finished the separated dyestuff is 110 filtered off, washed and dried. It represents when dry a garnet like powder, soluble in concentrated sulfuric acid with a violet-red color turning to bluish green when standin The new dyes-turf thus formed corresponds probably to the formula:

In order to produce this dyestuff on the vegetable fiber one may proceed as follows:

6 grs. of the anilide of 2.3-hydroxynaphthoic acid are well ground with 6 com. of Turkey red oil and 9 com. of a caustic soda solution of 34 Be. and they are dissolved by adding 90 com. of coiling water, then 96 com. of cold water, and at about C. 6 com. of formaldehyde of 33% are added. After about 5 to 10 minutes the whole is made up with cold water to 1 liter of liquor.

The cotton yarn is handled at about 30 for half an horn in this padding solution, centrifuged and then developed in the following bath:

2.63 grs. of -arnino-d-inethoxydiphenylamine sulfate are mixed with 10 com. of hot water and 3 corn. of hydrochloric acid of 20 then com. of ice water and 1.42 grs. of sodiurnnitrite are added and the mass is allowed to stand for half an hour while stir 'ing. Then 2.5 grs. of magnesium sulfate or the corresponding amount of zinc sulfate dissolved in water and 1 gr. of sodium bicarbonate are added and the whole is made up with cold water to 1 liter of liquor.

The padded material is treated in this developing solution for half an hour and well rinsed. A garnet dyeing is thus obtained. The dyestufi thus produced on the fiber is identical with the dyestuif of the aforesaid formula.

Example 2 Well boiled cotton yarn is impregnated with a solution containing 4 grs. of 2.3-hydroXynaphthoyli-chloroaniline, 10 com. of Turkey red oil and 8 coin. of a caustic soda solution of 34 and well wrun out. 22.8 grs. of l-aininm l'-ethozrydiphenyl diazotized with addition of sufficient amount of diluted hydrochloric acid 14 grs. of sodium nitrite simultaneously the nitrosocompound being formed, and the mass of diazotization is diluted until a concentration of a hundredth reel of diazocornpound in the liter.

To this solution of l-diazoi'-ethoxy-N-nitrosodiphenylarnine an amount of sodium bicarbonate until an almost neutral reaction is added and the impregnated cotton yar is therein developed, then cold and hot rinsed.

In this manner a garnet like dyeing of the dyestulf corresponding probably to formula:

Ezmmple 3 is obtained.

Well boiled cotton yarn is impregnated ith a solution containing Leeaaee is obtained.

Example 4 5 grs. of 2.3--hydroxynaphthoyl-4-toluidine, 5 of key red oil and 7.7 corn. of a caustic soda solu of 3d" in the liter, centrifuged inteiniediately rinsed for 5-10 minutes with a solution containing 3-0 grs. of common salt in the lit-er, then again well dehydrated.

The material is developed with a solution conhundredth. mol of i-diazo l-ethoXyuylaroine in the liter to which acetate is added and after soapat about 45 with a solution cona neutral soap in the lite and 5 rinsing it o a full garnet like dyeing of the dyestuff CgHsO l N=N Ezromple 5 3 grs. of 2.3hydroxynaphthoyle-toluidine are d with 6 coin. of a caustic soda solution 0 1 and ccrn. of Turkey red oil with addition or 3 coin. of formaldehyde and of one of t usual protective agents, for instance, 3 grs. l teetcl I double powder (of. Colour Index, page 353) to one liter of a padding solution. Silk yarn impregnated with this solution at 25 for a quarter of an hour, then 10 grs. cornnon salt are added per liter of liquor yarn is well dehydrated.

is developed in a bath neutralized with sodiun acetate and containing an amount of a 1.25 nethoxy-diphcnylainine after of an acetic acid of 50% and n salt per liter. thus produced on the fiber is identica with the dyestuif produced on cotton yarn according to Example 3.

i-annnoaddition of 5 c 10 grs. of co 1. Padding solution 15 grs. of 2.3-hydroxynaphthoyl-4-chloroaniline are well ground with 20 com. of Turkey red oil and 24 com. of a caustic soda solution of 34 B. and they are dissolved by adding 250 grs. of boiling water and boiling again the mass. Then the whole is made up with cold water to 1 liter.

2. Developing bath 16 grs. of 4-amino-4-methoxydipheny1arnine sulfate are stirred with com. of hot water and 25 com. of hydrochloric acid of 20 B., then 500 grs. of ice water and 8.5 grs. of sodium nitrite are added and the mass is allowed to stand for half an hour while stirrin Then 15 grs. of sodium acetate dissolved in water are added and the whole is made up with cold water to 1 liter.

The cotton piece goods are impregnated on a slop-padding machine with the aforesaid solution, squeezed out and intermediately dried in a given case.

Then the piece goods are developed on a padding machine at about 10 in the aforesaid developing bath and well rinsed. In this manner a deep red dyeing is obtained the produced dyestufi corresponding probably to the formula:

In the following table there are cited some further components suitable for the combination according to our process and the shades of dyeings obtained by the production on the fiber of the new dyestuffs which contain a nitrosogroup in their molecule:

- Shade of Combined with dyein g compound of obtained 4-aminodiphenylamine 2.3 hydroxynaphthoyl 2 Dark viochloroaniline let Do 2.3 hydroxynaphthoyl 4 Do. chloroaniline Do 2.3 hydroxynaphthoyl 2 Do. phenetidine Do 2.3 hydroxynaphthoyl 1 Do.

naphthylamine Do 2.3 hydroxynaphthoyl 4 Do.

chloro-2 anisidine Do 2.3 hydroxynaphthoyl 5 Do.

chloro-2-anisidine Do 2.3 hydroxynaphthoyl 2 Garnet aminodiphenyl-ether Do 2.3 hydroxynaphthoyl 4 Garnetaminophenylbenzylether brown Do Di-(2.3-hydroxynaphthoyD- o.

4.4 diamino 2.2.5.5 tetrachloro-diphenylurea Do 1 Bis 2.3 hydroxynaphthoyl Garnet dianisidine 4 amino 2 methyl 2.3-hydroxynaphthoyl-amino- Do.

diphenylamine hydroquinonedimethylether Do 2.3 hydroxynaphthoyl 5 Do.

chloro-2-amsidine Do -1 2.3 hydroxynaphthoyl 2 Do.

amino 3 naphtholmethylether 4-amino-2-methoxy- 2.3 hydroxynaphthoyl 4 Dark viodiphenylamine toluidine let Do 2.3 hydroxynaphthoyl 3 Do. phenetidine Do 2.3 hydroxynaphthoyl 2 Do.

naphthylamine Do 2.3 hydroxynaphthoyl 2 Do.

amino-ethyl-benzene Do 2.3 hydroxynaphthoyl 2 Garnet amino 3 naphtholmethylether 4 amino 2 ethoxy 2.3 hydroxynaphthoyl 3 Dark viodiphenylamine chloroaniline let Do-" 2.3 hydroxynaphthoyl 2 D0.

naphthylamine D0 2.3 hydroxynaphthoyl 4 Do.

ch1oro-2-anisidine D0 2.3 hydroxynaphthoyl 2 D0.

amino 4 chloro l ethylbenzene Shade of Dlazo-nitroso- Combined with dyeing compound of obtained 4..amin .2'-phen xy- 2.3 hydroxynaphthoyl 4 Dark viodiphenylamine toluidme let Do 2-3 hydroxynaphthoyl 2 D phenetidine Do hydroxynaphthoyl 3 D0. chloroaniline 4 amino 2' chloro y 9 Y phth0y1 a Reddish diphenylamine mtroanrlme d a r k violet D 2.3 hydroxynaphthoyl 4 0. chloroaniline D 2.3 hydroxynaphthoyl 4 D0.

amino-l-ethylbenzene D 2.3 hydroxynaphthoyl 1 Do.

naphthylamine 4 amino 3' t l 2.3 hydroigynaphthoyl 2 Garnet diphenylamine chloroamlme v 1 D 2.3 hydroxynaphthoyl 5 D0.

chloro-2-anisidine 4 amino 3' h1 2.3 hydroxynaphthoyl 3 Dark viodiphenylamine luldme let Do hydroxynaphthoyl 2 D phenetidine Dc 2.3 hydroxynaphthoy1 2 ammo 3 naphtholmethylether 4 amino 4 methyl hydroxynaphthoyl 4 Garnet diphenylaminc tolllldllle D 2-3 hydroxynaphthoyl 4 Do. chloroaniline D 2.3 hydroxynaphthoyl 5 Do.

chloro-Z-toluidine D 2 3 hydroxynaphthoyl 2 Do.

naphthylamine 4-amino-4-methoxyhyd y p y 2 Do.

diphenylamine tolllldlfle Do 2.3 hvdroxynaphthoyl 4 D0.

anisidine D 2.3 hydroxynaphthoyl 3 Do. chloroaniline D0 2.3 hydroxynaphthoyl 2 D0.

naphthylamine 4. .4 2.3 hydroxynaphthoyl 3 Claret diphenylaming amino-acetophenone D 2 3 hydroxynaphthoyl 3 Do.

amino 4 methcxybenzenesulfonic acid dimethylamide D 2.3 hydroxynaphthoyl 2 Do.

amino tolyl 4 ethylsulfone D 6 bromo 2.3 hydroxynaph- Dark viothoylaniline let D 6-brom0 -2.3-hydroxynaph- D thoyl 5 chloro 2 anisidine 4 amino 4 ethoxy- 2.3; hydroxynaphthoyl ani- Garnet diphenylamine llne D 2.3 hydroxynaphthoyl 2 Do.

luidine Do 2.3 hydroxynaphthoyl 3 Do.

toluidine Do 2.3 hy oxynaphthoyl 4 Do.

anisidine D0 2.3 hydroxynaphthoyl 3 Do. chloroaniline Do 2.3 hydroxynaphthoyl 2 Do. naphthylamine Do 6 bromo 243 hydroxynaph- Dark viothoyl-2-anisidine. let

Do 6 bromo 2.3 hydroxynaph- Dark garthoyl-l-naphthylamine not Do Di- (2.3-hydroxynaphthoyD- Reddish 2.5 diamino 4 methoxy brown l-toluene Do Di- (2.3-hydroxynaphthoyD- Garnet 4.4 diamino 2.2 dimethyl-diphenyl-methane Do Di- (2.3-hydroxynaphthoyl) Reddish 4.4-diaminobenzophenone garnet 4 amino 4 chloro 2.3 hydroxynaphthoyl 2 Dark viodiphenylamine anisidine let Do 2.3 hydroxynaphthoyl 4 Do.

anisidine Do 2.3 hydroxynaphthoyl 5 Do.

chl0ro-2-anisidine Do 2.3 hydroxynaphthoyl 2 Do,

naphthylamine Do 2.3 hydroxynaphthoyl 2 Do.

amino 3 naphtholmethylether 4-amino-4 -phenoxy- 2.3 hydroxynaphthoyl 4 D0.

diphenylamine phenetidine Do 2.3 hydroxynaphthoyl 4 Do.

chloroaniline Y Do 2.3 hydroxynaphthoyl 1 Do.

naphthoylamine 4 amino 3 methyl 2.3 hydroxynaphthoyl ani- Garnet 4 methoxy diline phenylamine Do 2.3 hydroxynaphthoyl 4 D0,

' chloroaniline 1 1 2.3 hydroxynaphthoyl 2 Do.

naphthylamme Shade of D1azo-n1trosocompound of Combined with ogygiixnegd 4 amino 3'- methyl 2.3 hydroxy-naphthoyl 4 Garnet 4 methoxy di anisidine phenylamine Do 2 3 hydroxynaphthoyl 2 B lu 1 s h toluidine garnet D0 2.3 hydroxynaphthoyl 2 Do. chloroaniline Do 2.3 hydroxynaphthoyl 3 Do. chloroaniline 4 amino 3 methyl 2.3 hy roxynaphthoyl 3 Dark vio- 6 methoxy diluldine let phenylamine Do 2.3 hydroxynaphthoyl 5 Garnet chloro-2-anisidine Do 2.3 hydroxynaphthoyl 1 Do.

naphthylaniine 4 amino 2 methyl 2.3 hydroxynaphthoyl 3 D0.

4 chloro diphenyltoluidine amine Do 2.3 hydroxynaphthoyl 3 Do.

nitroaniline Do 2.3 hydroxynaphthoyl ami- Do.

nohydroquinonedimethyl ether 4 amino 2 methyl hygiloxynaphthoyl 4 Dark vio- 5 chloro diphenyltoluldlne let amine Do 2.3 hydroxynaphthoyl 1 Do.

naphthylamine Do l. 2.3 hydroxynaphthoyl 2 Garnet naphthylamine 4 -amino 3'-methyl 2.3 hydroxynaphthoyl 5 Do.

6 chloro diphenylchloro-2-anisidine amine Do 3 ydroxynaphthoyl 2 Claret amino 4 chloro 1 ethylbenzene Do 3 ydroxynaphthoyl 1 Garnet 4 -amino 4' methyl 3 chloro diphenylamine 4 amino 2 Inethoxy 4 chloro diphenylamine 4 amino 3 methoxy 6.2 dimethyl 4 chloro diphenylam ine 4 amino 3.4' di chlorodiphenylamine 4 amino pheuyl B naphthylamine 4 amino 3.2 di methoxy diphenyl amine 4 amino 3.2 di methyl diphenylam ine 4 amino 3.2 di chloro diphenyl amine naphthylamine 2.3 hydroxynapthoylanilina 2.3 hydroxynaphthoyl 2 naplithylamine 2.3 hydroxynaphthoyl-aniline 2.3 hg'droxynaphthoyl 3 tolui ine 2.3 hydroxynaphthoyl 3 anisidine 2.2%; hydroxynaphthoyl ani- 2.3 hydroxynaphthoyl p anisidine 2.3 hydroxynaphthoyl m chloroaniline.

2.3 hydroxynaphthoyl 1 naphthylamine 2.3 hydroxynaphthoyl 2 naphthylarnine 2.3 hydroxynaphthoyl 4 chloroaniline 2.3 hydroxynaphthoyl 5 chloro-2-toluidine 2.3 hydroxynaphthoyl aminohydroquinone dirnethylether 2.3 hydroxynaphthoyl ani line 23 hydroxynaphthoyl 2 naphthylamine 2.3 hydroxynaphthoyl 2 toluidine 2.3 hydroxynaphthoyl 2 anisidine 2.3 hydroxynaphthoyl 4 chloroaniline 2.1}; hydroxynaphthoyl aniinc 2.3 hydroxynaphthoyl 2 naphthylamine 2.3 hydroxynaphthoyl 5 chloro-2-toluidine 2.3 hydroxynaphthoyl aminohydroquinone dimethylether Dark viclet G arnet Brownishgarnet Dark v10- let D0.

Dark garnet Garnet like claret Do.

Deep

gar-

The dyestuffs forming the subject of the present invention can be also produced by a printing process according to one of the usual methods.

In the following claims we understand under the combining process the combination of the components in substance as well as on a substratum, particularly on the fiber.

We claim:

1. The azodyestuffs containing a nitrosogroup and corresponding probably to the general formula:

lTIO

in which formula the naphthalene nucleus may contain a halogen and the two benzene nuclei halogen, alkyl-, oxalkylor oXaryl-groups, and R stands for a radical of the benzene or naphthalene series, which dyestuiTs are when dry redlike claret to garnet colored powders, soluble in concentrated sulfuric acid with a reddish-violet to violet color, forming valuable color lakes when mixed with the usual substrata and yielding claret to garnet-like reddish to violet dyeings of a good fastness to chlorine and washing when produced on the fiber.

2. Fiber dyed with the dyestuffs claimed in claim 1.

3. A process which comprises combining an N-nitroso-diphenylamine-4-diazonium salt of the general formula:

in which formula X means an acid radical of the salt and the two benzene nuclei may contain halogen, alkyloxalkylor oxarylgroups, with an arylamide of 2.3-hydroxynaphthoic acid, the aryl radical of which is of the benzene or naphthalene series, the naphthalene nucleus of which may contain a halogen atom.

4. The azodyestuffs containing a nitrosogroup and corresponding probably to the general formula:

claret to garnet-like reddish to violet dyeings ii of a good fastness to chlorine and washing when produced on the fiber.

5. Fiber dyed with the dyestuffs claimed in claim 4.

6. A process which comprises combining an llll N-nitroso-diphenylamine-4-diazonium the :general formulat p in which formula X means an acid radical of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and the two benzene nuclei may contain further substituents of the same group, withan arylamide of 2.3- hydroxynaphthoic acid, the aryl radical of which is of the benzene or naphthalene series, the naphthalene nucleus of which may contain a halogen atom. 7

,7. The azodyestuffs containing a nitrosogroup and corresponding probably to the general formula;

' in which formula Y means a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and R stands for a radical of the benzene or naphthalene series, which dyestuffs are when dry red-like claret to garnet colored powders, soluble in concentrated sulfuric acid with a reddish-violet to violet color; forming valuable color lakes when mixed with the usual substrate. and yielding claret to garnet-like reddish to violet dyeings of a good fastness to chlorine and washing when produced on the fiber.

8. Fiber dyed with the dyestuffs claimed in claim 7.

9. A process which comprises combining an N-nitroso-diphenylamine-4-diazonium salt of the general formula:

in which formula X means an acid radical of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, with an arylamide of 2.3-hydroxynaphthoic acid, the aryl radical of which is of the benzene or naphthalene series.

10. The azodyestufis containing a nitrosogroup and corresponding probably to the general formula:

in which formula Y means a substituent of the group consisting of halogen, alkyl, oxalkyl and oxaryl, and Z a substituent of the group consisting v of halogen, alkyl and oxalkyl, which dyestuifs are when dry red-like claret to garnet colored powders, soluble in concentrated sulfuric acid with a reddish-violet to violet color, forming valuable color lakes when mixed with the usual substrata and yielding claret to garnet-like reddish to violet dyeings of a good fastness to chlorine and washing when produced on the fiber.

11. Fiber dyed with the dyestufis claimed in claim 10.

the general formula:

in which formula X means an acid radical of the salt and Y a substituent of the group consisting of halogen, alkyl, oxalkyl and .oxarylfwith an arylarnide of 2.3-hy droxynaphthoic acidlof the.

formula wherein Z is a substituent of the group consisting of halogen, alkyl andoxalkyl.

13. The azodyestuffs containing a nitrosogroup and corresponding probably to the formula: V

IITO

in which formula X means an acid radical of the salt, with an arylamide or 2.3-hydroxynaphthoic acid of the formula:

H v o oNn z, wherein Z is a substituent of the group consisting of halogen, alkyl or oxalkyl.

16. The azodyestuff containing a nitrosogroup and corresponding probably to the formula:

which dyestuff is when dry a garnet colored powder, soluble in concentrated sulfuric acid with a violet color, forming valuable color lakes when mixed with the usual substrata and yielding salt 0 f" "12. A process which comprises combining an N -n itroso-diphenylaminel-diazonium 1 .salt of garnet like dyeings of a good fastness to chlorine and washing when produced on the fiber.

17. Fiber dyed with the dyestufif claimed in claim 16.

18. A process which comprises combining an 4-methoxy-N-nitroso-dipheny1amine 4 diazonium salt of the formula:

wherein X means an acid radical of the salt, with 2.3-hydroxynaphthoyl-4-chloro-aniline.

19. The azodyestufi containing a nitrosogroup and corresponding probably to the formula:

which dyestufi is when dry a garnet colored powder, forming valuable color lakes when mixed with the usual substrata and yielding garnet dyeings when produced on the fiber.

20. The azodyestufi containing a nitrosogroup and corresponding probably to the formula:

BIIO 

